Hydrophobic Silane Coating for Preventing Conductive Anodic Filament (CAF) Growth in Printed Circuit Boards

ABSTRACT

An enhanced substrate for making a printed circuit board (PCB) includes a hydrophobic silane coating of a silane composition intermixed with a silane coupling agent applied to a glass fiber substrate. The silane coupling agent is applied to the surface of the substrate for coupling the substrate to a varnish coating. Applying the silane coupling agent to the surface of the substrate creates surface silanols, which are implicated in conductive anodic filament (CAF) growth. A silane composition, which reacts with the surface silanols, is applied to the surface of the substrate having the silane coupling agent applied thereto to form the hydrophobic silane coating. The surface presented by the hydrophobic silane coating/substrate is hydrophobic and essentially silanol-free. This surface is then dried, and varnish is applied thereto. Then, the substrate, hydrophobic silane coating and varnish are subjected to curing conditions to define the PCB.

BACKGROUND OF THE INVENTION

1. Field of Invention

The present invention relates in general to coated glass fibersubstrates for use in making printed circuit boards (PCBs). Moreparticularly, the present invention relates to preventing conductiveanodic filament (CAF) growth in PCBs through an enhanced substrate thatincludes a hydrophobic silane coating of a silane composition intermixedwith a silane coupling agent applied to a glass fiber substrate.

2. Background Art

The basic concept behind a coupling agent is to join two disparatesurfaces. In the case of printed circuit boards (PCBs), a silanecoupling agent is often used to join a varnish coating (e.g., anepoxy-based resin) to a substrate (e.g., glass cloth) to define alaminate, or laminated structure. The silane coupling agent typicallyconsists of an organofunctional group to bind to the varnish coating anda hydrolyzable group that binds to the surface of the substrate. Inparticular, the alkoxy groups on the silicon hydrolyze to silanols,either through the addition of water or from residual water on thesurface of the substrate. Subsequently, the silanols react with hydroxylgroups on the surface of the substrate to form a siloxane bond (Si—O—Si)and eliminate water.

For the specific case of epoxy-based laminates, the organofunctionalgroup that has been found to exhibit desirable performance based onnumerous criteria is vinylbenzylaminoethylaminopropyl and alsobenzylaminoethylaminopropyl. Silane coupling agents, which include thisorganofunctional group, are thought to covalently bond to the epoxidefunctional groups of the traditional epoxy-based resin, such as the wellknown FR4 epoxy resins, through the secondary nitrogens of the aminogroups. While a plethora of silane coupling agents exists, the industryworkhorse for coupling epoxy-based resins has beenvinylbenzylaminoethylaminopropyl-trimethoxysilane (commerciallyavailable as Dow Corning Z-6032).

The PCB industry has recently migrated away from the traditional FR4epoxy based resins (due to lead-free requirements and the highersoldering temperatures associated with tin-silver-copper alloys). Hence,current varnish coatings are typically no longer comprised of FR4epoxies, rather they are more likely to be bismaleimide triazine (BT)resins or polyphenylene oxide/trially-isocyanurate (PPO/TAIC)interpenetrating networks. Typically,vinylbenzylaminoethylaminopropyltrimethoxysilane, originally developedfor traditional FR4 epoxies, is still the coupling agent utilized tocouple, or bond, the glass cloth substrate to the laminate varnish.However, other silane coupling agents have been proposed for use inmaking high-temperature PCBs. For example, U.S. patent application Ser.No. 12/694,005, to Gelorme et al., entitled “SILANE COUPLING AGENTS FORPRINTED CIRCUIT BOARDS”, filed Jan. 26, 2010, which is acontinuation-in-part of U.S. patent application Ser. No. 12/391,500, toGelorme et al., entitled “SILANE COUPLING AGENTS FOR PRINTED CIRCUITBOARDS”, filed Feb. 24, 2009, discloses such silane coupling agents,including diallylpropylisocyanuratetrimethoxysilane.

One problem experienced with PCBs is conductive anodic filament (CAF),which results from copper dissolution that emanates from the anode of acircuit and “grows” subsurface toward the cathode, frequently alongseparated glass fiber/varnish coating interfaces. With PCBs,anode/cathode pairs are typically plated through holes. CAF formationcauses a number of reliability issues and can result in catastrophicfailure of PCBs, which in some instances can cause fires. The bondbetween the varnish and substrate is understood to be an importantfactor in CAF, as is the presence of water in the varnish/substrateinterface.

Generally, in locations on PCBs where there are sources of copper, anelectrical bias, glass fiber, and moisture, potential exists for theformation of CAF. Typically, CAF occurs at the interface where the glassfiber has delaminated from the varnish, which creates a path for waterdiffusion. The reason this path is commonly associated with CAFformation is due to the exposure of surface silanols on the glassfibers. Silanols always exist on the surface of the glass fiber and,thus, there is always a pathway for the formation of CAF. Delaminationdoes not have to occur to create this pathway. Additionally, CAF canoccur from pre-existing water adsorbed onto the surface of the glassfiber (i.e., water may be deposited during processing of the glassfibers).

Surface silanols, as mentioned above, always exist on the surface of theglass fiber. These surface silanols are reacted when silane couplingagents, such as vinylbenzylaminoethylaminopropyltrimethoxysilane ordiallylpropylisocyanuratetrimethoxysilane, are utilized to couple, orbond, the glass cloth substrate to the laminate varnish. As noted above,the alkoxy groups on the silicon of the silane coupling agent hydrolyzeto silanols, either through the addition of water or from residual wateron the surface of the substrate. Subsequently, the silanols react withhydroxyl groups on the surface of the substrate to form a siloxane bond(Si—O—Si) and eliminate water. Unfortunately, residual alkoxy groups onthe silane coupling agent hydrolyze and create more silanols. Thus, moresurface silanols are created by the silane coupling agent.

For example, when diallylpropylisocyanuratetrimethoxysilane is used asthe silane coupling agent, even though the propyl group to which thetrialkoxysilane is attached is hydrophobic (retarding ingress of waterto the resin/glass interface and improving CAF resistance), surfacesilanols are nonetheless created. These surface silanols still provide ahydrophilic path for water diffusion, which leads to CAF formation.

Prior solutions to prevent CAF have typically used the addition ofsurface modifiers such as n-octyltrimethoxysilane and3-methacryloxypropyltrimethysilane, but the addition of these silanesrequires CO₂ reactors which operate at high pressures that are typicallyunsafe for large scale production. Additionally, the silanes used inthis process create silanols, which still provide a hydrophilic path forwater diffusion that ultimately leads to CAF formation. Although thisprocess does reduce the likelihood of CAF formation, CAF inevitablyoccurs nonetheless due to the silanes used as surface modifiers.

Other prior solutions to prevent CAF using coated fiber strands are setforth in U.S. Patent Application Publication No. 2002/0058140 A1, toDana et al., entitled “GLASS FIBER COATING FOR INHIBITING CONDUCTIVEANODIC FILAMENT FORMATION IN ELECTRONIC SUPPORTS”, published May 16,2002. For example, the abstract of the above-referenced published patentapplication describes the use of a resin compatible coating compositionon the surface of glass fibers, the resin compatible coating compositioncomprising (a) a plurality of discrete particles comprising a silicatehaving a high affinity for metal ions; and (b) at least one film-formingmaterial. As disclosed in the above-referenced published patentapplication, particles containing copper getters are imbedded in apolymeric coating. Hence, this solution attempts to prevent themigration of copper through the polymeric coating containing theparticles. However, this solution does nothing to address the moistureat the glass fiber/resin interface. By not treating this aspect, a pathfor CAF still exists. Additionally, the particles imbedded into thepolymer coating will never come into intimate contact with the glassfiber and, thus, these particles will not effectively minimize coppermigration. Also, there would be a finite amount of copper which could begettered before the copper getters would become saturated with copperand no longer act as copper getters. Reaching this saturation pointwould create yet another path for CAF formation.

In another solution disclosed in the above-referenced published patentapplication, the particles in the resin compatible coating compositioncan also be formed from hydrophobic polymeric materials to reduce orlimit moisture absorption by the coated strand. These particles arecontained within a secondary layer which is applied over a primary layerof a primary sizing composition (silane coupling agent). Even though theparticles in the secondary layer can be formed from hydrophobicpolymeric material, surface silanols are nonetheless created by theunderlying primary layer. These surface silanols still provide ahydrophilic path for water diffusion, which leads to CAF formation.

Moreover, the solutions disclosed in the above-referenced publishedpatent application would be plagued with several other problems such asbeing thick (several microns), exhibiting a different thermal expansionthan glass fiber, creating another interface for delamination to occur,severely changing glass cloth manufacturing, as well as being costly andcomplicated in that a number of materials are required just to preparethe resin compatible coating.

Therefore, a need exists for an enhanced mechanism for preventingconductive anodic filament (CAF) growth in printed circuit boards(PCBs).

SUMMARY OF THE INVENTION

According to the preferred embodiments of the present invention, anenhanced substrate for making a printed circuit board (PCB) includes ahydrophobic silane coating of a silane composition intermixed with asilane coupling agent applied to a glass fiber substrate. The silanecoupling agent is applied to the surface of the substrate for couplingthe substrate to a varnish coating. Applying the silane coupling agentto the surface of the substrate creates surface silanols, which areimplicated in conductive anodic filament (CAF) growth. A silanecomposition, which reacts with the surface silanols, is applied to thesurface of the substrate having the silane coupling agent appliedthereto to form the hydrophobic silane coating. The surface presented bythe hydrophobic silane coating/substrate is hydrophobic and essentiallysilanol-free. This surface is then dried, and varnish is appliedthereto. Then, the substrate, hydrophobic silane coating and varnish aresubjected to curing conditions to define the PCB.

BRIEF DESCRIPTION OF THE DRAWINGS

The preferred exemplary embodiments of the present invention willhereinafter be described in conjunction with the appended drawings,where like designations denote like elements.

FIG. 1 is a block diagram illustrating a portion of a printed circuitboard (PCB) in which a hydrophobic silane coating to prevent conduciveanode filament (CAF) formation in accordance with the preferredembodiments of the present invention is provided between a varnishcoating and a glass fiber substrate having its surface modified by asilane coupling agent.

FIG. 2 is a flow diagram illustrating a method for applying, via vaporphase deposition, a silane composition to form a hydrophobic silanecoating that prevents conducive anode filament (CAF) formation in aprinted circuit board (PCB) made in accordance with the preferredembodiments of the present invention.

FIG. 3 is a flow diagram illustrating a method for applying, viaimmersion into a silane/hydrocarbon solvent solution, a silanecomposition to form a hydrophobic silane coating that prevents conduciveanode filament (CAF) formation in a printed circuit board (PCB) made inaccordance with the preferred embodiments of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

1. Overview

In accordance with the preferred embodiments of the present invention,an enhanced substrate for making a printed circuit board (PCB) includesa hydrophobic silane coating of a silane composition intermixed with asilane coupling agent applied to a glass fiber substrate. The silanecoupling agent is applied to the surface of the substrate for couplingthe substrate to a varnish coating. Applying the silane coupling agentto the surface of the substrate creates surface silanols, which areimplicated in conductive anodic filament (CAF) growth. A silanecomposition, which reacts with the surface silanols, is applied to thesurface of the substrate having the silane coupling agent appliedthereto to form the hydrophobic silane coating. The surface presented bythe hydrophobic silane coating/substrate is hydrophobic and essentiallysilanol-free. This surface is then dried, and varnish is appliedthereto. Then, the substrate, hydrophobic silane coating and varnish aresubjected to curing conditions to define the PCB.

2. Detailed Description

In accordance with the preferred embodiments of the present invention, asilane composition is applied to the surface of a glass fiber substrate(to which a silane coupling agent was earlier applied) to form ahydrophobic silane coating, which is an intermixed layer containing bothsilanes. That is, the silane composition in accordance with thepreferred embodiments of the present invention is applied post silanecoupling agent addition.

FIG. 1 is a block diagram illustrating a portion of a printed circuitboard (PCB) 100 in which a hydrophobic silane coating 130 to preventconducive anode filament (CAF) formation in accordance with thepreferred embodiments of the present invention is provided between avarnish coating 140 and a glass fiber substrate 110 having its surfacemodified by a silane coupling agent. The hydrophobic silane coating 130is an intermixed layer containing both the silane composition and thesilane coupling agent.

The substrate 110 is conventional and may be any suitable substrate thatincludes glass fiber. For example, the substrate 110 may be woven glasscloth.

The varnish coating 140 is conventional and may be any suitable organicor inorganic surface coating. For example, the varnish coating 140 maybe an FR4 epoxy resin, a bismaleimide triazine (BT) resin, or apolyphenylene oxide/trially-isocyanurate (PPO/TAIC) interpenetratingnetwork.

The silane coupling agent is conventional and may be any suitable silanecoupling agent. The silane coupling agent typically consists of anorganofunctional group to bind to the varnish coating 140 and ahydrolyzable group that binds to the surface of the substrate 110. Forexample, the silane coupling agent may bevinylbenzylaminoethylaminopropyltrimethoxysilane ordiallylpropylisocyanuratetrimethoxysilane. Typically, the silanecoupling agent is a mono-layer thick.

In accordance with the preferred embodiment of the present invention,the hydrophobic silane coating 130, which is an intermixed layercontaining both silanes, is hydrophobic (water repelling). Consequently,a water droplet resting on the hydrophobic silane coating 130 willexhibit a high contact angle (i.e., at least 90°). The hydrophobicsilane coating 130 is preferably a mono-layer thick.

The silane composition used to form the hydrophobic silane coating 130in accordance with the preferred embodiments of the present inventionincludes a silane having a general formula structure R₁—S—R₍₂₋₄₎,wherein R₁ is a functional group that is reactive with alcohols, waterand/or surface silanols, and wherein R₂, R₃ and R₄ are each a functionalgroup that is hydrophobic and non-reactive (i.e., R₂, R₃ and R₄ are eachnon-reactive with the alcohols, water and/or surface silanols with whichR₁ is reactive). Examples of suitable silanes for the silane compositionin accordance with the preferred embodiments of the present inventioninclude (without limitation) chlorotrimethylsilane (i.e., (CH₃)₃SiCl,also known as trimethylsilylchloride or TMSCl), hexamethyldisilazane(i.e., [(CH₃)₃)Si]₂NH, also known as HMDS or HMDZ),perfluorooctyl-1H,1H,2H,2H-dimethylchlorosilane (i.e., C₁₀H₁₀ClF₁₃Si),and (3,3,3-trifluoropropyl)dimethyl-chlorosilane (i.e., C₅H₁₀ClF₃Si);and combinations thereof.

Silane(s) used to produce the hydrophobic silane coating in accordancewith the preferred embodiments of the present invention react withadsorbed water on the surface of the substrate, thus dehydrating alladsorbed water accumulated during fiber processing. Once the glasssurface is dehydrated, these silanes then react with surface silanolscreating a hydrophobic surface. The hydrophobic surface will preventwater diffusion into the interface between the varnish coating (which issubsequently applied in the process of making a printed circuit board)and the glass fiber in the printed circuit board. Even if delaminationbetween the varnish coating and the glass fiber occurs in the printedcircuit board, the normally hydrophilic glass fiber is hydrophobic, thuseliminating the most commonly associated path for CAF formation.

In accordance with the preferred embodiments of the present invention,silane(s) to prevent CAF formation (i.e., the silane(s) in the silanecomposition) can be added after the silane coupling agent has beenapplied. The addition of these silanes to prevent CAF formation, in oneembodiment (shown in FIG. 2, described below), can be achieved by vapordeposition on the surface of the glass fibers, which may advantageouslyremove the need for the use of solvents.

Alternatively, in another embodiment (shown in FIG. 3, described below),the glass fibers can be surface modified with the silane(s) to preventCAF formation using simple wet chemistry methods in a suitablehydrocarbon solvent or other suitable anhydrous solvent (typically,without the need for any additional catalyst). This allows the processto be tailored to a plethora of existing glass fiber modificationprocesses. Examples of suitable hydrocarbon solvents include (withoutlimitation) heptanes, hexanes, pentanes, xylenes, cyclohexane andtoluene; and combinations thereof.

Once the glass fibers have been treated with the silane(s) to preventCAF formation, there will be no build up of adsorbed water during fiberprocessing. Even if delamination occurs as a result of thermal expansionof the varnish coating (which is subsequently applied in the process ofmaking a printed circuit board), the glass fiber will remainhydrophobic—thereby preventing a path for CAF formation. Addition of thesilane(s) to prevent CAF formation does not leave any residual silanols(such residual silanols are associated with prior approaches).

FIG. 2 is a flow diagram illustrating a method 200 for applying, viavapor phase deposition, a silane composition to form a hydrophobicsilane coating that prevents conducive anode filament (CAF) formation ina printed circuit board (PCB) made in accordance with the preferredembodiments of the present invention. In the method 200, the stepsdiscussed below (steps 210-260) are performed. These steps are set forthin their preferred order. It must be understood, however, that thevarious steps may occur at different times relative to one another thanshown, or may occur simultaneously. Moreover, those skilled in the artwill appreciate that one or more of the steps may be omitted.

Method 200 begins when a substrate that includes glass fiber is cleaned(step 210). The substrate is conventional and may be any suitablesubstrate that includes glass fiber. For example, the substrate may bewoven glass cloth. The substrate is cleaned utilizing any suitableconventional cleaning process, such as the industry standard process forcleaning woven glass fabric described below.

Glass fiber is typically received at the glass weaver on a bobbin andcontains a sizing agent typically present at approximately 1.5 wt % ofthe glass filament. The sizing agent is a starch and oil-basedformulation that serves as an anti-static and slip agent which impartsstrength to the fabric during the weaving process. The glass filament tobe woven in the machine direction may contain 1 wt % PVA to impartadditional mechanical strength during the warping process. Followingweaving, the fabric is cleaned via an industry standard process:

1) The fabric is wound on a mandrel and subjected to temperatures inexcess of 500 C for several hours (a process known to those skilled inthe art as “carmelizing” as the fabric takes on a golden brown color).

2) Mandrels are subsequently subjected to temperatures greater than 200C for several days (in order to permit the temperature in the center ofthe core to equilibrate with the temperature of the fabric surface).

3) The fabric is permitted to cool to ambient temperature overnight.

The method 200 continues with modification of the surface of thesubstrate with a silane coupling agent (step 220). The silane couplingagent is conventional and may be any suitable silane coupling agent. Forexample, the silane coupling agent may bevinylbenzylaminoethylaminopropyltrimethoxysilane ordiallylpropylisocyanuratetrimethoxysilane. The silane coupling agent isapplied to the surface of the substrate using any suitable conventionalsurface modification process.

Steps 210 and 220 may be omitted in favor of obtaining a conventionalglass fiber substrate having its surface already modified with a silanecoupling agent. Such surface modified glass fiber substrates arecommercially available from glass weavers. The surface modificationprocesses utilized by these glass weavers may include elements that areconsidered proprietary to the glass weaver.

Typical process parameters of conventional surface modificationprocesses include the addition of a surfactant to a silane bath (i.e.,typically, the glass fabric is dipped in a silane bath) to enhancewetting of the glass fabric as well as prevent foaming. The silanecoupling agent concentration in the silane bath may be as high as 1 wt%, for example, though it is typically much less. The silane bath istypically acidic (pH 3-5) to prevent self-condensation of the silane.

In one exemplary conventional surface modification process, the glassfabric may be dipped into 0.1%-0.5% silane coupling agent/water solution(or water-ethanol solution), and then air-dried. The glass fabric maythen be placed in a desiccator at 110-120 C for 5-10 minutes to cure thesilane coupling agent on the surface of the substrate.

In another conventional surface modification process, an alcoholsolution is used for silylating the surface of the substrate with asilane coupling agent. A 2% silane solution can be prepared in asuitable alcohol (e.g., methanol, ethanol, isopropanol, and the like).The surface of the substrate can be wiped, dipped, or sprayed with thissolution. If the substrate is dipped into the solution, a sufficientsubmersion time (e.g., one or two minutes) may be necessary to allowsilane migration to the surface of the substrate. The substrate is thendried (e.g., air-dried). After the surface of the substrate dries,excess material can be gently wiped, or briefly rinsed off with alcohol.The layer of silane coupling agent may then be cured on the surface ofthe substrate for 5-10 minutes at 110 C, or for 24 hours at ambienttemperature.

The method 200 may continue with the drying of the surface of thesubstrate (i.e., the treated glass fabric) in preparation for vaporphase addition of a silane composition (step 230). For example, thetreated glass fabric may be dried at 110-120 C for 5-10 minutes.However, step 230 may be at least partially performed as part of step220, discussed above, when the silane coupling agent is cured on thesurface of the substrate.

Once the glass fiber has been treated with a silane coupling agent, alarge portion of the surface silanols remain. This leaves the surfacehydrophilic (water loving) and more likely to increase the chance of CAFformation.

The prior art recognized that a moderate cure cycle (110 C/15 minutes)will leave silanol groups remaining in free form. See, for example,Gerald L. Witucki, “A Silane Primer: Chemistry and Applications ofAlkoxy Silanes”, Journal of Coating Technology, Vol. 65, No. 822, pages57-60, July 1993. However, the prior art mistakenly classified thesesurface silanols as advantageous (rather than as a potentially ruinouspath for CAF formation) because the silanols may bond with thesubsequent top coat, forming an interpenetrating polymer network (IPN)and providing an improved adhesion.

By treating the surface with a silane composition in accordance with thepresent invention, the remaining surface silanols will be reacted withand removed. Also, by treating the surface silanols with a silanecomposition in accordance with the present invention, the surface willbecome extremely hydrophobic (water repelling). Not only will the use ofa silane composition in accordance with the present invention removesurface silanols, but it will also react with and remove any adsorbedwater on the surface of the glass fibers preventing another path for CAFformation.

The method 200 then continues by placing the substrate (i.e., thetreated and dried glass fabric) in a vapor phase of a silane compositionin accordance with the present invention (step 240). To modify thesurface of a glass fiber with a silane composition in accordance withthe present invention using vapor phase deposition techniques, thesubstrate must be passed through or placed within a chamber that allowsfor the silane composition to build up a vapor pressure. Such vapordeposition techniques are well known by those skilled in the art.

The silane composition in accordance with the present invention includesa silane having a general formula structure R₁—S—R₍₂₋₄₎, wherein R₁ is afunctional group that is reactive with alcohols, water and/or surfacesilanols, and wherein R₂, R₃ and R₄ are each a functional group that ishydrophobic and non-reactive (i.e., R₂, R₃ and R₄ are each non-reactivewith the alcohols, water and/or surface silanols with which R₁ isreactive). Examples of suitable silanes for the silane composition inaccordance with the preferred embodiments of the present inventioninclude (without limitation) chlorotrimethylsilane (i.e., (CH₃)₃SiCl,also known as trimethylsilylchloride or TMSCl), hexamethyldisilazane(i.e., [(CH₃)₃)Si]₂NH, also known as HMDS or HMDZ),perfluorooctyl-1H,1H,2H,2H-dimethylchlorosilane (i.e., C₁₀H₁₀ClF₁₃Si),and (3,3,3-trifluoropropyl)dimethyl-chlorosilane (i.e., C₅H₁₀ClF₃Si);and combinations thereof.

The vapor pressure can range from 0.1 to 1000 mm Hg, preferably 0.5 to500 mm Hg and most preferably 2 to 7 mm Hg of vapor pressure. Thefollowing example is for purposes of illustration and is non-limiting.In this (non-limiting) example, silane vapor is generated by placing thesilane or a silane/hydrocarbon solvent solution (utilizes the partialpressure contribution of the hydrocarbon solvent mixed with the silane)in a reservoir below the surface to be coated. The reservoir is heatedto generate the vapor pressure. If the silane has a low vapor pressure,vacuum can be applied to the chamber to increase the vapor concentrationof the silane. The substrate, as it is coated, is typically maintainedat an elevated temperature ranging from 25 C to 150 C, preferably 35 Cto 125 C and most preferably 45 C to 90 C. The duration the substrate isexposed to the vapor phase of the silane composition can range, forexample, from 0.1 to 1440 minutes, preferably 0.5 to 180 minutes andmost preferably 2 to 30 minutes, depending on the final silane surfacecoverage desired. The hydrophobic silane coating is preferably amono-layer thick. Those skilled in the art will appreciate, however,that the final silane surface coverage desired will vary depending onthe particular application. Also, it may be desirable to apply catalyst(e.g., amines) to the vapor phase of the silane composition to increasethe rate of reaction, which in turn may permit a reduction in theduration of exposure of the substrate to the vapor phase.

Once removed from the chamber, the coated substrate (i.e., hydrophobicsilane coating/substrate) is dried using any suitable conventionalmethodology known to those skilled in the art (step 250). For example,the coated substrate may be dried at 110-120 C for 5-10 minutes. Becausethe surface of the coated substrate is hydrophobic, any residual waterthereon is easily and completely removed during step 250.

The coated substrate (i.e., hydrophobic silane coating/substrate) maythen be further processed using conventional PCB fabrication techniques(step 260). For example, a conventional varnish (e.g., FR4 epoxy resins,bismaleimide triazine (BT) resins, polyphenyleneoxide/trially-isocyanurate (PPO/TAIC) interpenetrating networks, and thelike) may be applied to the coated substrate using any suitableconventional methodology known to those skilled in the art. After whichthe laminate is subjected to curing conditions, e.g., heated undervacuum, as known in the art, which results in a crosslinked phase thatis covalently bound to the glass fibers to define a laminate, orlaminated PCB. The hydrophobic surface of the coated substrate willprevent water diffusion into the interface between the varnish coatingand the glass fiber in the laminated PCB. Even if delamination betweenthe varnish coating and the glass fiber occurs in the PCB, the normallyhydrophilic glass fiber is hydrophobic, thus eliminating the mostcommonly associated path for CAF formation.

FIG. 3 is a flow diagram illustrating a method 300 for applying, viaimmersion into a silane/hydrocarbon solvent solution, a silanecomposition to form a hydrophobic silane coating that prevents conduciveanode filament (CAF) formation in a printed circuit board (PCB) made inaccordance with the preferred embodiments of the present invention. Inthe method 300, the steps discussed below (steps 310-350) are performed.These steps are set forth in their preferred order. It must beunderstood, however, that the various steps may occur at different timesrelative to one another than shown, or may occur simultaneously.Moreover, those skilled in the art will appreciate that one or more ofthe steps may be omitted.

Method 300 begins when a substrate that includes glass fiber is cleaned(step 310). The substrate is conventional and may be any suitablesubstrate that includes glass fiber. For example, the substrate may bewoven glass cloth. The substrate is cleaned utilizing any suitableconventional cleaning process, such as the industry standard process forcleaning woven glass fabric described below.

Glass fiber is typically received at the glass weaver on a bobbin andcontains a sizing agent typically present at approximately 1.5 wt % ofthe glass filament. The sizing agent is a starch and oil-basedformulation that serves as an anti-static and slip agent which impartsstrength to the fabric during the weaving process. The glass filament tobe woven in the machine direction may contain 1 wt % PVA to impartadditional mechanical strength during the warping process. Followingweaving, the fabric is cleaned via an industry standard process:

1) The fabric is wound on a mandrel and subjected to temperatures inexcess of 500 C for several hours (a process known to those skilled inthe art as “carmelizing” as the fabric takes on a golden brown color).

2) Mandrels are subsequently subjected to temperatures greater than 200C for several days (in order to permit the temperature in the center ofthe core to equilibrate with the temperature of the fabric surface).

3) The fabric is permitted to cool to ambient temperature overnight.

The method 300 continues with modification of the surface of thesubstrate with a silane coupling agent (step 320). The silane couplingagent is conventional and may be any suitable silane coupling agent. Forexample, the silane coupling agent may bevinylbenzylaminoethylaminopropyltrimethoxysilane ordiallylpropylisocyanuratetrimethoxysilane. The silane coupling agent isapplied to the surface of the substrate using any suitable conventionalsurface modification process.

Steps 310 and 320 may be omitted in favor of obtaining a conventionalglass fiber substrate having its surface already modified with a silanecoupling agent. Such surface modified glass fiber substrates arecommercially available from glass weavers. The surface modificationprocesses utilized by these glass weavers may include elements that areconsidered proprietary to the glass weaver.

Typical process parameters of conventional surface modificationprocesses include the addition of a surfactant to a silane bath (i.e.,typically, the glass fabric is dipped in a silane bath) to enhancewetting of the glass fabric as well as prevent foaming. The silanecoupling agent concentration in the silane bath may be as high as 1 wt%, for example, though it is typically much less. The silane bath istypically acidic (pH 3-5) to prevent self-condensation of the silane.

In one exemplary conventional surface modification process, the glassfabric may be dipped into 0.1%-0.5% silane coupling agent/water solution(or water-ethanol solution), and then air-dried. The glass fabric maythen be placed in a desiccator at 110-120 C for 5-10 minutes to cure thesilane coupling agent on the surface of the substrate.

In another conventional surface modification process, an alcoholsolution is used for silylating the surface of the substrate with asilane coupling agent. A 2% silane solution can be prepared in asuitable alcohol (e.g., methanol, ethanol, isopropanol, and the like).The surface of the substrate can be wiped, dipped, or sprayed with thissolution. If the substrate is dipped into the solution, a sufficientsubmersion time (e.g., one or two minutes) may be necessary to allowsilane migration to the surface of the substrate. The substrate is thendried (e.g., air-dried). After the surface of the substrate dries,excess material can be gently wiped, or briefly rinsed off with alcohol.The layer of silane coupling agent may then be cured on the surface ofthe substrate for 5-10 minutes at 110 C, or for 24 hours at ambienttemperature.

Once the glass fiber has been treated with a silane coupling agent, alarge portion of the surface silanols remain. This leaves the surfacehydrophilic (water loving) and more likely to increase the chance of CAFformation.

The prior art recognized that a moderate cure cycle (110 C/15 minutes)will leave silanols groups remaining in free form. See, for example,Gerald L. Witucki, “A Silane Primer: Chemistry and Applications ofAlkoxy Silanes”, Journal of Coating Technology, Vol. 65, No. 822, pages57-60, July 1993. However, the prior art mistakenly classified thesesurface silanols as advantageous (rather than as a potentially ruinouspath for CAF formation) because the silanols may bond with thesubsequent top coat, forming an interpenetrating polymer network (IPN)and providing an improved adhesion.

By treating the surface with a silane composition in accordance with thepresent invention, the remaining surface silanols will be reacted withand removed. Also, by treating the surface silanols with a silanecomposition in accordance with the present invention, the surface willbecome extremely hydrophobic (water repelling). Not only will the use ofa silane composition in accordance with the present invention removesurface silanols, but it will also react with and remove any adsorbedwater on the surface of the glass fibers preventing another path for CAFformation.

The method 300 then continues by placing the substrate (i.e., thetreated glass fabric) in a silane surface modification bath containing asolution of a silane composition in accordance with the presentinvention and a suitable hydrocarbon solvent (step 330). Step 330 may beperformed via means known in the art, such as a dip coating process.

The silane composition in accordance with the present invention includesa silane having a general formula structure R₁—S—R₍₂₋₄₎, wherein R₁ is afunctional group that is reactive with alcohols, water and/or surfacesilanols, and wherein R₂, R₃ and R₄ are each a functional group that ishydrophobic and non-reactive (i.e., R₂, R₃ and R₄ are each non-reactivewith the alcohols, water and/or surface silanols with which R₁ isreactive). Examples of suitable silanes for the silane composition inaccordance with the preferred embodiments of the present inventioninclude (without limitation) chlorotrimethylsilane (i.e., (CH₃)₃SiCl,also known as trimethylsilylchloride or TMSCl), hexamethyldisilazane(i.e., [(CH₃)₃)Si]₂NH, also known as HMDS or HMDZ),perfluorooctyl-1H,1H,2H,2H-dimethylchlorosilane (i.e., C₁₀H₁₀ClF₁₃Si),and (3,3,3-trifluoropropyl)dimethyl-chlorosilane (i.e., C₅H₁₀ClF₃Si);and combinations thereof.

Examples of suitable hydrocarbon solvents include (without limitation)heptanes, hexanes, pentanes, xylenes, cyclohexane and toluene; andcombinations thereof.

The concentration of the silane can range from 0.01 to 100% (vol),preferably 0.05 to 10% (vol) and most preferably 0.1 to 3% (vol). Theduration the substrate is exposed to the silane surface modificationbath can range, for example, from 0.1 to 1440 minutes, preferably 0.5 to180 minutes and most preferably 2 to 30 minutes, depending on the finalsilane surface coverage desired. The hydrophobic silane coating ispreferably a mono-layer thick. Those skilled in the art will appreciate,however, that the final silane surface coverage desired will varydepending on the particular application.

Once removed from the bath, the coated substrate (i.e., hydrophobicsilane coating/substrate) is dried using any suitable conventionalmethodology known to those skilled in the art (step 340). For example,the coated substrate may be dried at 110-120 C for 5-10 minutes. Becausethe surface of the coated substrate is hydrophobic, any residual waterthereon is easily and completely removed during step 340.

The coated substrate (i.e., hydrophobic silane coating/substrate) maythen be further processed using conventional PCB fabrication techniques(step 350). For example, a conventional varnish (e.g., FR4 epoxy resins,bismaleimide triazine (BT) resins, polyphenyleneoxide/trially-isocyanurate (PPO/TAIC) interpenetrating networks, and thelike) may be applied to the coated substrate using any suitableconventional methodology known to those skilled in the art. After whichthe laminate is subjected to curing conditions, e.g., heated undervacuum, as known in the art, which results in a crosslinked phase thatis covalently bound to the glass fibers to define a laminate, orlaminated PCB. The hydrophobic surface of the coated substrate willprevent water diffusion into the interface between the varnish coatingand the glass fiber in the laminated PCB. Even if delamination betweenthe varnish coating and the glass fiber occurs in the PCB, the normallyhydrophilic glass fiber is hydrophobic, thus eliminating the mostcommonly associated path for CAF formation.

One skilled in the art will appreciate that many variations are possiblewithin the scope of the present invention. Thus, while the presentinvention has been particularly shown and described with reference topreferred embodiments thereof, it will be understood by those skilled inthe art that these and other changes in form and details may be madetherein without departing from the spirit and scope of the presentinvention.

1. An enhanced substrate for a printed circuit board (PCB), comprising:a substrate that includes glass fiber; and a hydrophobic silane coatingof a silane composition intermixed with a silane coupling agent appliedto the substrate, wherein the hydrophobic silane coating/substratepresents a surface that is hydrophobic and essentially silanol-free. 2.The enhanced substrate as recited in claim 1, wherein the substratecomprises a sheet of woven glass fibers.
 3. The enhanced substrate asrecited in claim 1, wherein the hydrophobic silane coating is formed byapplying a silane composition to the surface of the substrate having thesilane coupling agent applied thereto, wherein the silane compositionincludes a silane having a general structure R₁—S—R_((2,3,4)), whereinR₁ is a functional group that is reactive with one or more surfacesilanols created when the silane coupling agent is applied to thesurface of the substrate, and wherein R₂, R₃ and R₄ are each afunctional group that is hydrophobic and non-reactive with the one ormore surface silanols.
 4. The enhanced substrate as recited in claim 1,wherein the hydrophobic silane coating is formed by applying a silanecomposition to the surface of the substrate having the silane couplingagent applied thereto, and wherein the silane composition includes asilane selected from a group consisting of chlorotrimethylsilane,hexamethyldisilazane, perfluorooctyl-1H,1H,2H,2H-dimethylchlorosilane,and (3,3,3-trifluoropropyl)dimethyl-chlorosilane; and combinationsthereof.
 5. The enhanced substrate as recited in claim 1, wherein thehydrophobic silane coating is a monolayer thick.
 6. The enhancedsubstrate as recited in claim 1, further comprising a varnish coating onthe surface presented by the hydrophobic silane coating/substrate,wherein the silane coupling agent couples the varnish coating to thesubstrate.
 7. A printed circuit board (PCB) comprising at least oneenhanced substrate according to claim
 6. 8. A method of making anenhanced substrate for a printed circuit board, comprising the steps of:providing a substrate that includes glass fiber; applying a silanecoupling agent to the surface of the substrate, wherein the surface ofthe substrate having the silane coupling agent applied thereto includesone or more surface silanols; and applying a silane composition to thesurface of the substrate having the silane coupling agent appliedthereto to form a hydrophobic silane coating comprising an intermixedlayer of the silane composition and the silane coupling agent, whereinthe silane composition reacts with the one or more surface silanols, andwherein the hydrophobic silane coating/substrate presents a surface thatis hydrophobic and essentially silanol-free.
 9. The method as recited inclaim 8, wherein the substrate comprises a sheet of woven glass fibers.10. The method as recited in claim 8, wherein the silane compositionincludes a silane having a general structure R₁—S—R_((2,3,4)), whereinR₁ is a functional group that is reactive with alcohols, water and/orthe one or more surface silanols, and wherein R₂, R₃ and R₄ are each afunctional group that is hydrophobic and non-reactive with the alcohols,water and/or the one or more surface silanols with which R₁ is reactive.11. The method as recited in claim 8, wherein the silane compositionincludes a silane selected from a group consisting ofchlorotrimethylsilane, hexamethyldisilazane,perfluorooctyl-1H,1H,2H,2H-dimethylchlorosilane, and(3,3,3-trifluoropropyl)dimethyl-chlorosilane; and combinations thereof.12. The method as recited in claim 8, wherein the hydrophobic silanecoating is a monolayer thick.
 13. The method as recited in claim 8,wherein the step of applying the silane composition includes the stepsof: drying the surface of the substrate having the silane coupling agentapplied thereto; after the step of drying the surface of the substratehaving the silane coupling agent applied thereto, placing the substratehaving the silane coupling agent applied thereto in a vapor phase of thesilane composition to form the hydrophobic silane coating by vapordeposition; after the step of placing the substrate in a vapor phase ofthe silane composition, drying the surface presented by the hydrophobicsilane coating/substrate.
 14. The method as recited in claim 8, whereinthe step of applying the silane composition includes the steps of:placing the substrate having the silane coupling agent applied theretoin a solution of the silane composition and a hydrocarbon solvent; afterthe step of placing the substrate having the silane coupling agentapplied thereto in a solution of the silane composition in a hydrocarbonsolvent, drying the surface presented by the hydrophobic silanecoating/substrate.
 15. A method of making a printed circuit board (PCB),comprising the steps of: providing a substrate that includes glassfiber; applying a silane coupling agent to the surface of the substrate,wherein the surface of the substrate having the silane coupling agentapplied thereto includes one or more surface silanols; applying a silanecomposition to the surface of the substrate having the silane couplingagent applied thereto to form a hydrophobic silane coating comprising anintermixed layer of the silane composition and the silane couplingagent, wherein the silane composition reacts with the one or moresurface silanols, and wherein the hydrophobic silane coating/substratepresents a surface that is hydrophobic and essentially silanol-free;after the step of applying a silane composition, drying the surfacepresented by the hydrophobic silane coating/substrate; after the dryingstep, applying a varnish over the surface presented by the hydrophobicsilane coating/substrate, wherein the silane coupling agent couples thevarnish coating to the substrate; and subjecting the substrate, thehydrophobic silane coating and the varnish to curing conditions so as todefine a PCB.
 16. The method as recited in claim 15, wherein thesubstrate comprises a sheet of woven glass fibers.
 17. The method asrecited in claim 15, wherein the silane composition includes a silanehaving a general structure R₁—S—R₍₂₋₄₎, wherein R₁ is a functional groupthat is reactive with alcohols, water and/or the one or more surfacesilanols, and wherein R₂, R₃ and R₄ are each a functional group that ishydrophobic and non-reactive with the alcohols, water and/or the one ormore surface silanols with which R₁ is reactive.
 18. The method asrecited in claim 15, wherein the silane composition includes a silaneselected from a group consisting of chlorotrimethylsilane,hexamethyldisilazane, perfluorooctyl-1H,1H,2H,2H-dimethylchlorosilane,and (3,3,3-trifluoropropyl)dimethylchlorosilane; and combinationsthereof.
 19. The method as recited in claim 15, wherein the hydrophobicsilane coating is a monolayer thick.
 20. The method as recited in claim15, wherein the step of applying the silane composition includes thesteps of: drying the surface of the substrate having the silane couplingagent applied thereto; after the step of drying the surface of thesubstrate having the silane coupling agent applied thereto, placing thesubstrate having the silane coupling agent applied thereto in a vaporphase of the silane composition to form the hydrophobic silane coatingby vapor deposition.
 21. The method as recited in claim 15, wherein thestep of applying the silane composition includes the steps of: placingthe substrate having the silane coupling agent applied thereto in asolution of the silane composition and a hydrocarbon solvent.